EP0800117B1 - Toner zur Entwicklung elektrostatischer Bilder und Fixierverfahren - Google Patents

Toner zur Entwicklung elektrostatischer Bilder und Fixierverfahren Download PDF

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Publication number
EP0800117B1
EP0800117B1 EP97105412A EP97105412A EP0800117B1 EP 0800117 B1 EP0800117 B1 EP 0800117B1 EP 97105412 A EP97105412 A EP 97105412A EP 97105412 A EP97105412 A EP 97105412A EP 0800117 B1 EP0800117 B1 EP 0800117B1
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EP
European Patent Office
Prior art keywords
toner
polyester resin
acid
binder resin
toner according
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Expired - Lifetime
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EP97105412A
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English (en)
French (fr)
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EP0800117A1 (de
Inventor
Masaaki Taya
Kenji Okado
Ryoichi Fujita
Makoto Kanbayashi
Tsuyoshi Takiguchi
Wakashi Iida
Tetsuya Ida
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Canon Inc
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Canon Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/081—Preparation methods by mixing the toner components in a liquefied state; melt kneading; reactive mixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793—Crosslinked polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants

Definitions

  • the present invention relates to a toner for developing electrostatic images formed in image forming methods, such as electrophotography, electrostatic recording and electrostatic printing, and a fixing method for fixing the resultant toner image onto a transfer(-receiving) material under heat and pressure application.
  • a photoconductive insulating layer is uniformly charged and then exposed to form an electrostatic image; the electrostatic image is developed with a toner [developing step]; the resultant toner image is transferred onto a transfer(-receiving) material, such as transfer paper, via or without via an intermediate transfer member [transfer step]; and the toner image is fixed onto the transfer material under application of heat, pressure, or heat and pressure [fixing step].
  • the toner has to exhibit performances required in not only the developing step but also in the transfer and fixing steps.
  • a toner is generally subjected to mechanical abrasion due to mechanical shearing force and impact within a developing device and is therefore liable to be deteriorated during copying or printing on a large number of sheets, such as several thousands to several tens of thousands sheets.
  • Such toner deterioration may be prevented by using a tough binder resin having a large molecular weight sufficient to withstand the mechanical abrasion, but such a binder resin generally has a high softening point and requires a high heating roller temperature for sufficient fixing in the heat roller fixing scheme, which is a contact fixing scheme exhibiting a good heat efficiency and is widely used.
  • a high heating roller temperature is liable to cause a deterioration of the fixing device, the curling of paper after the fixation, and an increased energy consumption.
  • such a binder resin has a poor pulverizability and causes a lower toner production efficiency.
  • the heat roller fixing scheme exhibits remarkably good heat efficiency because the heating roller surface contacts the toner image surface on the transfer sheet (or fixing sheet) under pressure, and is therefore widely used from a low-speed system to a high-speed system.
  • the toner is liable to cause an offset phenomenon that the toner is attached onto the heating roller surface and the attached toner is transferred onto a subsequent transfer material.
  • JP-B Japanese Patent Publication
  • JP-A Japanese Laid-Open Patent Application
  • toners having improved anti-offset performances there have been proposed a toner using a covalently bonded crosslinked polymer or branch polymer inclusively called a crosslinked polymer obtained by using a polyfunctional monomer or a polyfunctional initiator (as disclosed in JP-A 3-203746 and JP-A 4-24648), a toner using an ionically bonded crosslinked polymer obtained by intimately bonding a metal oxide and a polymer (as disclosed in JP-A 61-213858 and JP-A 6-175395).
  • These toners all may have an improved anti-offset characteristic but the resultant polymer is caused to suffer from a lowering in fixability inherent to the binder resin and is accompanied with strong entanglement of polymer molecules.
  • the crosslinked resin component as represented by a tetrahydrofuran-insoluble matter makes difficult the dispersion of a colorant or a charge control agent within the binder resin and results in a lower pulverizability of kneaded product during toner production.
  • the lowest fixation or fixable temperature of a toner is present between a lower-side offset temperature and a higher-side offset temperature, so that the operable temperature region is defined between the lowest fixation temperature and the higher-side offset temperature. Accordingly, if the lowest fixation temperature is lowered as low as possible and the high-temperature offset initiation temperature is elevated as high as possible, the operable temperature region can be broadened. As a result, it becomes possible to effect energy economization, high-speed fixation and prevention of paper curling. The suppression of paper curling allows satisfactory copying on both sides of paper, intelligent-mode operation of a copying machine, accurate temperature control of a fixing device and broadening of tolerable temperature range.
  • the temperature within a developing device is liable to be elevated, so that the toner is required to exhibit a high-temperature storage stability which exceeds a level expected heretofore. Further, it has been also desired to provide a toner satisfying stable developing performance and good transferability in combination so as to output high-quality images.
  • a generic object of the present invention is to provide a toner for developing electrostatic images having solved the above-mentioned problems of a conventional toner and exhibiting excellent electrophotographic performances and fixability.
  • a more specific object of the present invention is to provide a toner for developing electrostatic images having a sufficient anti-offset characteristic while allowing a lower fixation temperature.
  • Another object of the present invention is to provide a toner for developing electrostatic images exhibiting a stable chargeability in various environmental conditions including high temperature - high humidity and low temperature - low humidity and allowing very faithful development of electrostatic images.
  • Another object of the present invention is to provide a toner for developing electrostatic images free from agglomeration even when left standing for a long time in a high temperature environment and capable of exhibiting similar developing performance as before the standing.
  • Another object of the present invention is to provide a toner for developing electrostatic images having excellent transferability.
  • Another object of the present invention is to provide a toner for developing electrostatic images capable of exhibiting an excellent covering power because of good dispersibility of colorant therein.
  • Another object of the present invention is to provide a heat and pressure fixing method allowing a broard fixation temperature range.
  • a toner for developing an electrostatic image comprising: toner particles containing at least a binder resin, a colorant and an organometallic compound; wherein
  • a fixing method comprising: fixing a toner image carried on a sheet material onto the sheet material under application of heat and pressure, wherein the toner image is formed of the above-mentioned toner.
  • Figure 1 is a storage modulus curve of an example toner according to the invention.
  • Figure 2 is a storage modulus curve of a comparative example toner.
  • Figure 3 shows a 13 C-NMR chart (partial) of an example polyester resin.
  • Figure 4 is a schematic illustration of an image forming apparatus to which a toner according to the present invention may be applied.
  • Figure 5 is a schematic illustration of an exemplary heat and pressure fixing device for fixing a toner image formed of a toner according to the invention onto a sheet material under application of heat and pressure.
  • Figure 6 illustrates an example of metal ion crosslinking of polyester polymer chains.
  • the toner comprises toner particles containing a binder resin having a THF-insoluble content of at most 5.0 wt. % based on the binder resin, has a glass transition temperature of 50 - 80 o C and has specific storage modulus characteristics.
  • the binder resin in the toner particles has a tetrahydrofuran-insoluble (THF-insoluble) content of at most 5.0 wt. % based on the binder resin,
  • a THF-insoluble content in the binder resin of at most 5.0 wt. %, preferably at most 1.0 wt. %, is effective for providing excellent low-temperature fixability and color mixing characteristic.
  • a glass transition temperature of the toner of 50 - 80 °C, preferably 51 - 75 °C, is effective for providing excellent low-temperature fixability, anti-blocking characteristic and storage stability.
  • the toner satisfies the specified storage modulus characteristics that the toner has G' 80 of 1x10 3 - 5x10 5 Pa (1x10 4 - 5x10 6 dyn/cm 2 ), preferably 2x10 3 - 1x10 5 Pa (2x10 4 - 1x10 6 dyn/cm 2 ), and a ratio (G' 80 /G' 130 ) of 10 - 5x10 3 , preferably 5x10 - 5x10 3 , and provides a storage modulus curve exhibiting a minimum (G'min) in a temperature region of 110 - 190 °C, preferably 115 - 170 °C.
  • the presence of a minimum G'min in a temperature region of 110 - 190 °C means that the toner exhibits a higher viscoelasticity at a temperature on a higher temperature side than the temperature giving the storage-modulus minimum G'min and is therefore effective for providing the toner with very excellent anti-high temperature offset characteristic.
  • G' 80 is 8 ⁇ 5 x 10 3 Pa (8.5x10 4 dyn/cm 2 )
  • G' 130 is 2 ⁇ 10 Pa (2x10 2 dyn/cm 2 )
  • the ratio (G' 80 /G' 130 ) is 4.25x10 2
  • G'min is present at a temperature of 144 °C and at a value of 1 ⁇ 5 x 10 Pa (1.5x10 2 dyn/cm 2 )
  • a storage modulus at 200 °C (G' 200 ) is 2 ⁇ 10 3 Pa (2x10 4 dyn/cm 2 ).
  • a toner having viscoelasticity characteristics as shown in Figure 1 is excellent in low-temperature fixability, color miscibility and anti-high temperature characteristic and exhibits a broad fixable temperature range.
  • a toner having viscoelasticity characteristics as represented by a storage modulus curve shown in Figure 2 does not show an explicit minimum in the temperature region of 110 - 190 o C and shows a storage modulus which monotonously decreases as temperature increases on a high temperature side.
  • Such a toner exhibits an inferior high-temperature offset characteristic and a narrower fixable temperature range than the toner according to the present invention.
  • the binder resin constituting the toner may preferably comprise a polymer having a carboxyl group or an acid anhydride group, or both of these.
  • the polymer may include styrene-acrylic copolymers, styrene-methacrylic copolymers and polyester resins. It is particularly preferred to use a polyester resin.
  • dihydric alcohol components for producing a polyester resin may include: ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenols derivatives represented by the following formula (A): wherein R denotes an ethylene or propylene group, x and y are independently an integer of at least 1 with the proviso that the average of x+y is in the range of 2 - 10.
  • polyhydric alcohol components having three or more functional groups may include: sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxybenzene.
  • Such a polyhydric alcohol may preferably be used in a proportion of 0.1 - 1.9 mol. % of total monomers for providing the polyester resin used.
  • dicarboxylic acid for producing a polyester resin may include: fumaric acid, maleic acid, maleic anhydride, succinic acid, adipic acid, sebacic acid, malonic acid, aliphatic acid monomers obtained by substituting a saturated or unsaturated hydrocarbon group having 8 - 22 carbon atoms for a hydrogen atom of the above-mentioned acids; and aromatic acid monomers, such as phthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid and ester derivatives of these acids.
  • polycarboxylic acids having three or more functional groups may include: 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and esters of these acids.
  • Such a polycarboxylic acid may preferably be used in a proportion of 0.1 - 1.9 mol. % of total monomers for producing the polyester resin used.
  • the polyester resin has a glass transition temperature (Tg) of 50 - 80 °C, more preferably 51 - 75 °C and may preferably provide a molecular weight distribution based on GPC (gel permeation chromatography) of its THF-soluble content such that it provides a number-average molecular weight (Mn) of 1000 - 9000, more preferably 1500 - 7500; a main peak molecular weight (Mp) of 5000 - 12000, more preferably 5500 - 11000; and a ratio Mw/Mn of weight-average molecular weight (Mw) to number-average molecular weight (Mn) of at most 5.0.
  • Tg glass transition temperature
  • Mn number-average molecular weight
  • Mp main peak molecular weight
  • Mw weight-average molecular weight
  • Mn number-average molecular weight
  • the polyester resin is in a non-linear form by using a poly-basic carboxylic acid having three or more functional groups or a polyhydric alcohol having three or more functional groups and has a THF-insoluble content of at most 1 wt. % based on the polyester resin.
  • Such a non-linear polyester resin may preferably be produced through a process including a first stage of subjecting a dibasic carboxylic acid or a dibasic carboxylic acid ester and a dihydric alcohol to polycondensation to form a linear prepolymer, and a second stage of subjecting the linear prepolymer, a dibasic carboxylic acid (or an ester thereof), a dihydric alcohol, a tri- or more-basic polycarboxylic acid (or an ester thereof) or a tri- or more-basic alcohol to polycondensation.
  • the polyester resin used in the present invention may preferably have an acid value of 1 - 30 kgKOH/g, more preferably 3 - 25 mgKOH/g so as to provide stable triboelectric chargeability and stable electrophotographic performances in various environments.
  • a particularly preferred class of polyester resin may include those having a molecular skeleton represented by the following formula (B): wherein x and y independently denote an integer of at least 1 providing an average of x+y in the range of 2 - 4.
  • the polyester resin having a molecular skeleton represented by the formula (B) may preferably be provided with a non-linear structure by using a polybasic carboxylic acid or a polyhydric alcohol.
  • Such a polyester resin having a molecular structure represented by the formula (B) may easily form a metal ion crosslinked structure when heated together with an organometallic compound to provide a toner exhibiting a storage modulus curve giving an explicit minimum G'min in the temperature region of 110 - 190 °C.
  • Such a polyester resin having a molecular structure represented by the formula (B) shows an excellent affinity with an organometallic compound and, based on the affinity, the molecular structure including ⁇ electrodes and oxygen atoms further donating electrons to the metal in the organometallic compound to provide a kind of coordination.
  • This effect is particularly pronounced in the case where the metal is aluminum. This is presumably because, when an aluminum atom forms three bonds in an organometallic compound, the aluminum atom is placed in a state lacking two electrons compared with an electron octet (including four electron pairs formed from 8 electrons), and the aluminum atom in the organometallic compound tends to have 8 electrons by receiving two more electrons.
  • M may represent Al.
  • a state as shown in Figure 6 may be formed by a metal such as Al or a metal having a valence of at least 2 together with a molecular skeleton shown in the formula (B).
  • This state may provide an entanglement between molecules based on a chemical affinity which is different from a conventional metal ion crosslinkage with a side or terminal carboxyl groups of a binder resin.
  • This state may provide a combination of low-temperature fixability and anti-high temperature offset characteristic not attained heretofore and provide the following functions and effects, particularly improved fixability and transfer efficiency.
  • a further preferred class of polyester resin may be a non-linear polyester resin including a molecular skeleton represented by formula -C-D-C-D, wherein C denotes (wherein x and y are integers of at least 1) and D denotes formed by connecting at least two molecular skeletons represented by the above formula (B) and non-linearized with a polycarboxylic acid or polyhydric alcohol each having three or more functional group.
  • Such a polyester resin having a molecular skeleton represented by the formula -C-D-C-D- may be produced by subjecting a bisphenol derivative represented by the following formula (E): wherein x and y are integers of at least 1 providing an average of x+y of 2 - 4, to polycondensation with fumaric acid to form a prepolymer, and subjecting the prepolymer to polycondensation with a diol, a dicarboxylic acid and a polycarboxylic acid or polyhydric alcohol each having three or more functional groups.
  • E bisphenol derivative represented by the following formula (E): wherein x and y are integers of at least 1 providing an average of x+y of 2 - 4, to polycondensation with fumaric acid to form a prepolymer, and subjecting the prepolymer to polycondensation with a diol, a dicarboxylic acid and a polycarboxylic acid or polyhydric alcohol each having three
  • a bisphenol derivative having a propoxy group like one represented by the following formula (F): does not show such a remarkable as described above presumably because of a steric hindrance due to the presence of methyl groups.
  • a molecular structure of the following formula (G): formed from ethylene glycol and terephthalic acid, and a molecular structure of the following formula (H): formed from ethylene glycol and fumaric acid also fail to exhibit such a remarkable effect as described above.
  • An example of 13 C-NMR chart is shown in Figure 3.
  • the integrated value TAC corresponds to the number of carbon atoms belonging to all the carboxyl groups in the polyester resin
  • the integrated value AC* corresponds to the number of carbon atoms belonging to the carboxyl group in within the molecular skeleton of the formula (B). If the peak area percentage is 10 - 70 %, the dispersibility of an organometallic compound (particularly, an aromatic carboxylic acid metal compound) within the polyester resin and the mutual reactivity between the organometallic compound and the polyester resin are well adjusted to further improve the low-temperature fixability, anti-high temperature offset characteristic and developing performance of the toner.
  • the organometallic compound used in the present invention may preferably be an organometallic compound of an aromatic carboxylic acid and a metal having a valence of at least 2.
  • Examples of the aromatic carboxylic acid may include three types represented by the following formulae: wherein R 1 - R 7 independently denote hydrogen atom, an alkyl group of 1 - 12 carbon atom, an alkenyl group of 2 - 12 carbon atoms, -OH, -NH 2 , -NH(CH 3 ), -N(CH 3 ) 2 , -OCH 3 , -OC 2 H 5 , -COOH or -CONH 2 .
  • R 1 may preferably be hydroxyl group, amino group or methoxy group, and hydroxyl group is most preferred.
  • the aromatic carboxylic acid may preferably be a dialkylsalicylic acid, such as di-tert-butylsalicylic acid.
  • the metal constituting the organometallic compound may preferably be a metal having a valence of at least 2.
  • divalent metal may include: Mg 2+ , Ca 2+ , Sr 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ , and Cu 2+ .
  • Zn 2+ , Ca 2+ , Mg 2+ and Sr 2+ are preferred.
  • metal having a valence of 3 or more may include: Al 3+ , Cr 3+ , Fe 3+ and Ni 3+ .
  • Al 3+ , Fe 3+ , Cr 3+ and Zn 2+ are preferred, and Al 3+ is particularly preferred.
  • the organometallic compound may particularly preferably be di-tert-butylsalicylic acid aluminum compound.
  • the aromatic carboxylic acid metal compound may for example be prepared by dissolving an aromatic carboxylic acid in a sodium hydroxide aqueous solution and adding thereto dropwise an aqueous solution containing a polyvalent metal atom, followed by stirring under heating, pH adjustment, cooling to room temperature, filtering out and washing with water.
  • the synthesis process is not restrictive.
  • the organometallic compound may preferably be used in an amount of 0.1 - 10 wt. parts, more preferably 0.5 - 9 wt. parts, per 100 wt. parts of the binder resin so as to adjust the viscoelastic properties and the triboelectric chargeability of the toner.
  • the toner according to the present invention can further contain a charge control agent, as desired, other than the above-mentioned organometallic compound so as to further stabilize the chargeability.
  • the charge control agent may be used in 0.1 - 10 wt. parts, more preferably 0.1 - 7 wt. parts, per 100 wt. parts of the binder resin.
  • Examples of the charge control agent may include: nigrosine and imidazole compounds.
  • the colorant used for constituting the toner according to the present invention may comprise a pigment and/or a dye.
  • the dye may include: C.I. Direct Red 1, C.I. Direct Red 4, C.I. Acid Red 1, C.I. Basic Red 1, C.I. Mordant Red 30, C.I. Direct Blue 1, C.I. Direct Blue 2, C.I. Acid Blue 9, C.I. Acid Blue 15, C.I. Basic Blue 3, C.I. Basic Blue 5, C.I. Mordant Blue 7, C.I. Direct Green 6, C.I. Basic Green 4, and C.I. Basic Green 6.
  • Examples of the pigment may include: Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Ca salt, eosine lake; Brilliant Carmine 3B; Manganese Violet, Fast Violet B, Methyl Violet Lake, Cobalt BLue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Pigment Green B, Malachite Green Lake, and Final Yellow Green G.
  • magenta pigment for providing a toner for full-color image formation may include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209; C.I. Pigment Violet 19; and C.I. Violet 1, 2, 10, 13, 15, 23, 29, 35.
  • the pigments may be used alone but can also be used in combination with a dye so as to increase the clarity for providing a color toner for full color image formation.
  • magenta dyes may include: oil-soluble dyes, such as C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21, 27; C.I. Disperse Violet 1; and basic dyes, such as C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
  • pigments include cyan pigments, such as C.I. Pigment Blue 2, 3, 15, 16, 17; C.I. Vat Blue 6, C.I. Acid Blue 45, and copper phthalocyanine pigments represented by the following formula and having a phthalocyanine skeleton to which 1 - 5 phthalimidomethyl groups are added:
  • yellow pigment may include: C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83; C.I. Vat Yellow 1, 13, 20.
  • Such a non-magnetic colorant may be added in an amount of 0.1 - 60 wt. parts, preferably 0.5 - 50 wt. parts, further preferably 1 - 15 wt. parts, per 100 wt. parts of the binder resin.
  • the magnetic toner particles may contain a magnetic material which can also function as a colorant.
  • the magnetic material may include: iron oxides, such as magnetite, hematite, and ferrite; iron oxides containing another metal oxide; metals, such as Fe, Co and Ni, and alloys of these metals with other metals, such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W and V; and mixtures of the above.
  • the magnetic material may include: triiron tetroxide (Fe 3 O 4 ), diiron trioxide ( ⁇ -Fe 2 O 3 ), zinc iron oxide (ZnFe 2 O 4 ), yttrium iron oxide (Y 3 Fe 5 O 12 ), cadmium iron oxide (CdFe 2 O 4 ), gadolinium iron oxide (Gd 3 Fe 5 O 12 ), copper iron oxide (CuFe 2 O 4 ), lead iron oxide (PbFe 12 O 19 ), nickel iron oxide (NiFe 2 O 4 ), neodymium iron oxide (NdFe 2 O 3 ), barium iron oxide (BaFe 12 O 19 ), magnesium iron oxide (MgFe 2 O 4 ), manganese iron oxide (MnFe 2 O 4 ), lanthanum iron oxide (LaFeO 3 ), powdery iron (Fe), powdery cobalt (Co), and powdery nickel (Ni).
  • Particularly suitable magnetic material for the present invention is fine powder of triiron tetroxide
  • the magnetic material may have an average particle size (Dav.) of 0.1 - 2 ⁇ m, preferably 0.1 - 0.5 ⁇ m.
  • the magnetic material may preferably show magnetic properties when measured by application of 10 kilo-Oersted, inclusive of: a coercive force (Hc) of 20 - 150 Oersted, a saturation magnetization ( ⁇ s) of 50 - 200 emu/g, particularly 50 - 100 emu/g, and a residual magnetization ( ⁇ r) of 2 - 20 emu/g.
  • Hc coercive force
  • ⁇ s saturation magnetization
  • ⁇ r residual magnetization
  • the magnetic material may be contained in the toner in a proportion of 10 - 200 wt. parts, preferably 20 - 150 wt. parts, per 100 wt. parts of the binder resin.
  • the toner particles constituting the toner according to the present invention may optionally contain one or more species of release agent.
  • the release agent may include: aliphatic hydrocarbon waxes, such as low-molecular weight polyethylene, low-molecular weight polypropylene, microcrystalline wax, and paraffin wax, oxidation products of aliphatic hydrocarbon waxes, such as oxidized polyethylene wax, and block copolymers of aliphatic hydrocarbon waxes; waxes containing aliphatic esters as principal constituents, such as carnauba wax, sasol wax, montanic acid ester wax, and partially or totally deacidified aliphatic esters, such as deacidified carnauba wax.
  • the release agent may include: saturated linear aliphatic acids, such as palmitic acid, stearic acid, and montanic acid; unsaturated aliphatic acids, such as brassidic acid, eleostearic acid and parinaric acid; saturated alcohols, such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols, such as sorbitol; aliphatic acid amides, such as linoleylamide, oleylamide, and laurylamide; saturated aliphatic acid bisamides, methylene-bisstearylamide, ethylene-biscaprylamide, and ethylene-bislaurylamide, and hexamethylene-bisstearylamide; unsaturated aliphatic acid amides, such as ethylene-bisolerylamide, hexamethylene-bisoleylamide, N,N'-dioleyladipoy
  • a particularly preferred class of wax may include aliphatic alcohol waxes and aliphatic hydrocarbon waxes.
  • the aliphatic alcohol waxes may preferably be those represented by the following formula (I): CH 3 (CH 2 ) x CH 2 OH wherein x is a positive number in the range of 20 - 250 as an average value.
  • Examples of the aliphatic hydrocarbon waxes may include: a low-molecular weight alkylene polymer wax obtained through polymerization of an alkylene by radical polymerization under a high pressure or in the presence of a Ziegler catalyst under a low pressure; an alkylene polymer obtained by thermal decomposition of an alkylene polymer of a high molecular weight; and a hydrocarbon wax obtained by subjecting a mixture gas containing carbon monoxide and hydrogen to the Arge process to form a hydrocarbon mixture and distilling the hydrocarbon mixture to recover a residue, optionally followed by hydrogen addition.
  • Fractionation of hydrocarbon wax may preferably be performed by the press sweating method, the solvent method, vacuum distillation or fractionating crystallization.
  • hydrocarbons As the source of the hydrocarbon wax, it is preferred to use hydrocarbons as obtained through synthesis from a mixture of carbon monoxide and hydrogen in the presence of a metal oxide catalyst (generally a composite of two or more species), hydrocarbons having up to several hundred carbon atoms synthesized by the Synthol process, the Hydrocol process (using a fluidized catalyst bed), and the Arge process (using a fixed catalyst bed) providing a product rich in waxy hydrocarbon; and hydrocarbons obtained by polymerizing an alkylene, such as ethylene, in the presence of a Ziegler catalyst, because they are saturated long-chain hydrocarbons with little branching. It is particularly preferred to use a wax synthesized from carbon monoxide and hydrogen because of its narrow molecular weight distribution.
  • a metal oxide catalyst generally a composite of two or more species
  • the wax may preferably have such a molecular weight distribution as to provide a main peak in a molecular weight region of 400 - 2400, more preferably 450 - 2000, particularly preferably 500 - 1600.
  • a wax having such a molecular weight distribution can provide the toner with a preferred thermal characteristic.
  • the release agent may be contained in 0.1 - 20 wt. parts, preferably 0.5 - 10 wt. parts, per 100 wt. parts of the binder resin.
  • the release agent may be blended with the binder resin, e.g., by dissolving the resin in a solvent and adding and mixing the release agent within the resultant solution at an elevated temperature under stirring, or by melt kneading the release agent together with the binder resin.
  • the toner particles may preferably be blended with a flowability-improving agent externally added thereto so as to exhibit an improved image forming characteristic.
  • Examples of such a flowability-improving agent may include: powder of fluorine-containing resin, such as polyvinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powdery silica such as wet-process silica and dry-process silica, fine powdery titanium oxide and fine powdery alumina and treated silica, treated titanium oxide or treated alumina obtained by surface-treating (hydrophobizing) such fine powdery silica, fine powdery titanium oxide or fine powdery alumina with silane coupling agent, titanium coupling agent, silicone oil, etc.
  • fluorine-containing resin such as polyvinylidene fluoride fine powder and polytetrafluoroethylene fine powder
  • fine powdery silica such as wet-process silica and dry-process silica, fine powdery titanium oxide and fine powdery alumina and treated silica, treated titanium oxide or treated alumina obtained by surface-treating (hydrophobizing) such fine powdery silica, fine powdery titanium oxide
  • the flowability-improving agent may have a specific surface area of at least 30 m 2 /g, preferably 50 m 2 /g, as measured by the BET method according to nitrogen adsorption.
  • the flowability-improving agent may be used in an amount of 0.01 - 8 wt. parts, preferably 0.1 - 4 wt. parts, per 100 wt. parts of the toner.
  • the toner particles may be prepared by sufficiently blending the binder resin(s), the colorant, the organometallic compound, and other optional additives, as desired, by a blender such as a Henschel mixer or a ball mill, followed by melt-kneading for mutual dissolution of the resins of the blend, cooling for solidification of the kneaded product, pulverization and classification to recover toner particles having a prescribed average particle size (diameter).
  • a blender such as a Henschel mixer or a ball mill
  • the toner particles may be further sufficiently blended with an external additive such as a flowability-improving agent by a blender such as a Henschel mixer to obtain a toner according to the present invention, wherein the external additive is carried on the surface of the toner particles.
  • an external additive such as a flowability-improving agent by a blender such as a Henschel mixer to obtain a toner according to the present invention, wherein the external additive is carried on the surface of the toner particles.
  • the toner according to the present invention may preferably have a weight-average particle size (diameter) of 2.5 - 10 ⁇ m, more preferably 2.5 - 6.0 ⁇ m so as to provide good image quality.
  • the toner may preferably have a volume-average particle size of 2.5 - 6.0 ⁇ m.
  • Physical parameters of a binder resin, toner particles and a toner referred to herein are generally based on values measured in the following manners.
  • Storage modulus G' is measured by using a visco-elasticity measurement apparatus ("Rheometer RDA-II", available from Rheometrics Co.) in a temperature range of 60 - 210 °C.
  • Shearing means A flat disk plate having a diameter of 7.9 mm for a high-modulus sample or 40 mm for a low-modulus sample each axially connected to a transducer is used in combination with a shallow cup having a flat bottom disposed opposite to the flat disk plate of a similar diameter (ca. 8 mm or 40 mm) and connected to an actuator and a vertical cylindrical brim for containing a sample therein to be covered with the flat disk plate which is disposed with a gap of ca. 2 mm from the bottom of and rotated relative to the shallow disk with a clearance of at most 0.5 mm from the upper brim (inner wall) of the shallow cup.
  • Measurement sample A toner is heat-melted and then molded into a disk sample having a diameter of ca. 7.9 mm and a height of 2 mm or a disk sample having a diameter of ca. 40 mm and a thickness of ca. 2 mm.
  • Initial value is set to 0.1 %, and the measurement is performed according to an automatic measurement mode.
  • Measurement temperature Increased at a rate of 2 °C/min, from 60 o C to 210 °C.
  • THF-insoluble content [(W 1 -W 2 )/W 1 ] x 100 (wt. %)
  • THF-soluble matter weight W 6 g in the sample.
  • the molecular weight (distribution) may be measured based on a chromatogram obtained by GPC (gel permeation chromatography).
  • a column is stabilized in a heat chamber at 40 °C, tetrahydrofuran (THF) solvent is caused to flow through the column at that temperature at a rate of 1 ml/min.
  • GPC sample solution is prepared in an amount of 50 - 200 ⁇ l and at a resin concentration of 0.05 - 0.6 wt. % and is injected into the column.
  • the identification of sample molecular weight and its molecular weight distribution is performed based on a calibration curve obtained by using several monodisperse polystyrene samples and having a logarithmic scale of molecular weight versus count number.
  • the standard polystyrene samples for preparation of a calibration curve may be available from, e.g., Pressure Chemical Co.
  • the detector may be an RI (refractive index) detector.
  • RI reffractive index
  • a preferred example thereof may be a combination of ⁇ -styragel 500, 10 3 , 10 4 and 10 5 available from Waters Co.; a combination of Shodex KF-801, 802, 803, 804, 805, 806 and 807 available from Showa Denko K.K.
  • Measurement may be performed in the following manner by using a differential scanning calorimeter ("DSC-7", available from Perkin-Elmer Corp.) according to ASTM D3418-82.
  • DSC-7 differential scanning calorimeter
  • the sample is placed on an aluminum pan and subjected to measurement in a temperature range of 30 - 200 o C at a temperature-raising rate of 10 °C/min in a normal temperature - normal humidity environment in parallel with a blank aluminum pan as a reference.
  • the glass transition temperature (Tg) is determined as a temperature of an intersection between a DSC curve and an intermediate line passing between the base lines obtained before and after the appearance of the absorption peak.
  • Coulter Counter TA-II or Coulter Multisizer II (available from Coulter Electronics Inc.) is used together with an electrolytic solution comprising a ca. 1 % NaCl aqueous solution which may be prepared by dissolving a reagent-grade sodium chloride or commercially available as "ISOTON-II" (from Counter Scientific Japan).
  • a surfactant preferably an alkyl benzenesulfonic acid salt
  • 2 - 20 mg of a sample is added into 10 to 150 ml of the electrolytic solution.
  • the resultant dispersion of the sample in the electrolytic solution is subjected to a dispersion treatment by an ultrasonic disperser for ca. 1 - 3 min., and then subjected to measurement of particle size distribution by using the above-mentioned apparatus equipped with a 100 ⁇ m-aperture.
  • the volume and number of toner particles are measured for respective channels to calculate a volume-basis distribution and a number-basis distribution of the toner. From the volume-basis distribution, a weight-average particle size (D 4 ) and volume-average particle size (Dv) of the toner or toner particles are calculated by using a central value as a representative for each channel.
  • the channels used include 13 channels of 2.00 - 2.52 ⁇ m; 2.52 - 3.17 ⁇ m; 3.17 - 4.00 ⁇ m; 4.00 - 5.04 ⁇ m; 5.04 - 6.35 ⁇ m; 6.35 - 8.00 ⁇ m; 8.00 - 10.08 ⁇ m, 10.08 - 12.70 ⁇ m; 12.70 - 16.00 ⁇ m; 16.00 - 20.20 ⁇ m; 20.20 - 25.40 ⁇ m; 25.40 - 32.00 ⁇ m: and 32.00 - 40.30 ⁇ m.
  • the color electrophotographic apparatus shown in Figure 4 is roughly divided into a transfer material (recording sheet)-conveying section I including a transfer drum 15 and extending from the right side (the right side of Figure 4) to almost the central part of an apparatus main assembly 1, a latent image-forming section II disposed close to the transfer drum 15, and a developing means (i.e., a rotary developing apparatus) III.
  • a transfer material recording sheet
  • a latent image-forming section II disposed close to the transfer drum 15
  • a developing means i.e., a rotary developing apparatus
  • the transfer material-conveying section I is constituted as follows.
  • an opening is formed through which are detachably disposed transfer material supply trays 2 and 3 so as to protrude a part thereof out of the assembly.
  • Paper (transfer material)-supply rollers 4 and 5 are disposed almost right above the trays 2 and 3.
  • paper-supply rollers 6 and the transfer drum 15 are disposed leftward thereof so as to be rotatable in an arrow A direction.
  • paper- supply rollers 6, a paper-supply guide 7 and a paper-supply guide 8 are disposed.
  • Adjacent to the outer periphery of the transfer drum 15, an abutting roller 9, a glipper 10, a transfer material separation charger 11 and a separation claw 12 are disposed in this order from the upstream to the downstream along the rotation direction.
  • a transfer charger 13 and a transfer material separation charger 14 are disposed inside the transfer drum 15 .
  • a portion of the transfer drum 15 about which a transfer material is wound about is provided with a transfer sheet (not shown) attached thereto, and a transfer material is closely applied thereto electrostatically.
  • a conveyer belt means 16 is disposed next to the separation claw 12, and at the end (right side) in transfer direction of the conveyer belt means 16, a fixing device 18 is disposed. Further downstream of the fixing device is disposed a discharge tray 17 which is disposed partly extending out of and detachably from the main assembly 1.
  • the latent image-forming section II is constituted as follows.
  • a photosensitive drum e.g., an OPC photosensitive drum
  • a latent image-bearing member rotatable in an arrow direction shown in the figure is disposed with its peripheral surface in contact with the peripheral surface of the transfer drum 15.
  • a discharging charger 20 there are sequentially disposed a cleaning means 21 and a primary charger 23 from the upstream to the downstream in the rotation direction of the photosensitive drum 19.
  • an imagewise exposure means including, e.g., a laser 24 and a reflection means like a mirror 25, is disposed so as to form an electrostatic latent image on the outer peripheral surface of the photosensitive drum 19.
  • the rotary developing apparatus III is constituted as follows. At a position opposing the photosensitive drum 19, a rotatable housing (hereinafter called a "rotary member") 26 is disposed. In the rotary member 26, four-types of developing devices are disposed at equally distant four radial directions so as to visualize (i.e., develop) an electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 19.
  • the four-types of developing devices include a yellow developing device 27Y, a magenta developing device 27M, a cyan developing apparatus 27C and a black developing apparatus 27BK.
  • the entire operation sequence of the above-mentioned image forming apparatus will now be described based on a full color mode.
  • the drum 19 is charged by the primary charger 23.
  • the moving peripheral speeds (hereinafter called "process speed") of the respective members, particularly the photosensitive drum 19, may be at least 100 mm/sec, (e.g., 130 - 250 mm/s).
  • the photosensitive drum 29 After the charging of the photosensitive drum 19 by the primary charger 23, the photosensitive drum 29 is exposed imagewise with laser light modulated with a yellow image signal from an original 28 to form a corresponding latent image on the photosensitive drum 19, which is then developed by the yellow developing device 27Y set in position by the rotation of the rotary member 26, to form a yellow toner image.
  • a transfer material (e.g., plain paper) sent via the paper supply guide 7, the paper supply roller 6 and the paper supply guide 8 is taken at a prescribed timing by the glipper 10 and is wound about the transfer drum 15 by means of the abutting roller 9 and an electrode disposed opposite the abutting roller 9.
  • the transfer drum 15 is rotated in the arrow A direction in synchronism with the photosensitive drum 19 whereby the yellow toner image formed by the yellow-developing device is transferred onto the transfer material at a position where the peripheral surfaces of the photosensitive drum 19 and the transfer drum 15 abut each other under the action of the transfer charger 13.
  • the transfer drum 15 is further rotated to be prepared for transfer of a next color (magenta in the case of Figure 4).
  • the photosensitive drum 19 is charge-removed by the discharging charger 20, cleaned by a cleaning blade or cleaning means 21, again charged by the primary charger 23 and then exposed imagewise based on a subsequent magenta image signal, to form a corresponding electrostatic latent image.
  • the electrostatic latent image is formed on the photosensitive drum 19 by imagewise exposure based on the magenta signal
  • the rotary member 26 is rotated to set the magenta developing device 27M in a prescribed developing position to effect a development with a magenta toner. Subsequently, the above-mentioned process is repeated for the colors of cyan and black, respectively, to complete the transfer of four color toner images.
  • the four color-developed images on the transfer material are discharged (charge-removed) by the chargers 22 and 14, released from holding by the glipper 10, separated from the transfer drum 15 by the separation claw 12 and sent via the conveyer belt 16 to the fixing device 18, where the four-color toner images are fixed under heat and pressure.
  • a series of full color print or image formation sequence is completed to provide a prescribed full color image on one surface of the transfer material.
  • the fixing speed of the fixing device 18 is slower (e.g., at 90 mm/s) than the peripheral speed (e.g., 160 mm) of the photosensitive drum. This is in order to provide a sufficient heat quantity for melt-mixing yet un-fixed images of two to four toner layers.
  • an increased heat quantity is supplied to the toner images.
  • a fixing roller 29 as a fixing means comprises a 5 mm-thick aluminum-made core metal (or cylinder) 31 coated successively with a 2 mm-thick RTV (room temperature vulcanization-type) silicone rubber layer 32 and a 230 ⁇ m-thick HTV (high temperature vulcanization-type) silicone rubber layer 33, and has a diameter of 60 mm.
  • RTV room temperature vulcanization-type silicone rubber
  • HTV high temperature vulcanization-type
  • a pressure roller 30 as a pressing means comprises a 5 mm-thick aluminum-made core metal (or cylinder) 34 coated successively with a 2 mm-thick RTV silicone rubber layer 35, a 50 ⁇ m-thick fluorine rubber layer 58 and a 230 ⁇ m-thick HTV silicone rubber layer 60, and has a diameter of 60 ⁇ m.
  • the fixing roller 29 is provided with a halogen heater 36 as a heating means disposed therein, and the pressure roller 30 is also provided with a halogen heater 37 therein so as to allow heating from both sides.
  • the temperatures of the fixing roller 29 and the pressure roller 30 are detected by thermistors 38a and 38b abutted against the fixing roller 29 and the pressure roller 30. Based on the detected temperatures, the halogen heaters 36 and 37 are controlled by control units 39a and 39b, respectively, thereby controlling the fixing roller 29 and the pressing roller 30 respectively at constant temperatures (e.g., 160 o C ⁇ 10 °C).
  • the fixing roller 29 and the pressure roller 30 are pressed against each other at a total pressure of ca. 40 kg by a pressurizing mechanism (not shown).
  • the fixing device further includes an oil application device O as a release agent application means, a cleaning device C, and a cleaning blade C1 for removing oil and dirt attached to the pressure roller 30.
  • the oil application device applies, e.g., dimethylsilicone oil 41 (e.g., "KF 96 300cs", made by Shink-Etsu Kagaku K.K.) onto the fixing roller 29 via an oil-scooping roller 42 and an oil applicator roller 43 while controlling the oil application amount by a controller blade 44.
  • dimethylsilicone oil 41 e.g., "KF 96 300cs", made by Shink-Etsu Kagaku K.K.
  • the cleaning device C cleans the fixing roller 29 by abutting a web of nonwoven cloth (e.g., "Nomex", available from E.I. Du Pont) against the fixing roller 29 by means of a pressing roller 45.
  • the web is wound up about a take-up roller at an appropriate rate by a control drive mechanism (not shown) so as to prevent the pile up of toner, etc., at the abutting position with the fixing roller 29.
  • a transfer material carrying a fixed full-color image on one surface thereof is sent to a discharge tray 17 via paper discharge rollers 52.
  • paper re-feed rollers 50 are disposed so as to feed the transfer material once placed on the discharge tray 17 again to the latent image-forming section II, and a conveying page 51 for conveying the transfer materials is disposed downstream of the paper re-feed rollers 50.
  • the transfer materials on the discharge tray are fed again by the paper re-feed rollers 50 and passed through the conveying passage 51 to the latent image-forming section for-forming a color image on the back sides thereof.
  • a transfer material carrying a fixed color image on one side and carrying a non-fixed color toner image is conveyed up to the fixing roller 29 and the pressure roller 30 to be fixed thereat, and is finally conveyed to the discharge tray 17 to complete color image formation on both sides of the transfer material.
  • the toner according to the present invention is excellent in low-temperature fixability and anti-high temperature offset characteristic, so that the application amount of a release agent can be reduced, and the cleaning device is less soiled.
  • a toner image formed of the toner according to the present invention may preferably be fixed by a heat and pressure fixation mode at a fixing roller surface temperature in the range of 150 °C ⁇ 30 °C.
  • diol components of the following formulae E and P having different average values of x+y were used for producing polyester resins.
  • the above monomers were subjected to polycondensation to form a linear prepolymer having a number-average molecular weight (Mn) of 720.
  • Polyester Resin (1) The properties of Polyester Resin (1) are summarized in Table 1 appearing hereinafter together with those of Polyester Resins (2) - (15) prepared in the following Production Examples.
  • Diol component (E-1) 10 mol.% Fumaric acid 10 mol.%
  • Diol component (E-1) 30 mol.% Fumaric acid 30 mol.%
  • Diol component (E-2) of Formula E (x+y 2.2) 5 mol.% Fumaric acid 5 mol.%
  • Diol component (E-3) of Formula E (x+y 2.3) 8 mol.% Fumaric acid 8 mol.%
  • Diol component (E-4) of Formula E (x+y 4.0) 5 mol.% Fumaric acid 5 mol.%
  • Diol component (E-5) of Formula E (x+y 3.1) 15 mol.% Fumaric acid 15 mol.%
  • Diol component (E-6) of Formula E (x+y 3.8) 8 mol.% Fumaric acid 8 mol.%
  • Diol component (E-7) of Formula E (x+y 1.0) 15 mol.% Diol component (P-1) 36 mol.% Fumaric acid 35 mol.% Terephthalic acid 14 mol.% Trimellitic acid 1 mol.%
  • Diol component (P-1) 50 mol.% Fumaric acid 49 mol.% Trimellitic acid 1 mol.%
  • Diol component (E-1) 5 mol.%
  • Diol component (P-1) 45 mol.% Fumaric acid 4 mol.% Terephthalic acid 45 mol.% Trimellitic acid 1 mol.%
  • Diol component (E-9) of Formula E (x+y 5.1) 14 mol.% Diol component (P-1) 37 mol.% Fumaric acid 38 mol.% Terephthalic acid 10 mol.% Trimellitic acid 1 mol.%
  • Diol component (E-10) of Formula E (x+y 3.0) 51 mol.% Fumaric acid 20 mol.% Terephthalic acid 20 mol.% Trimellitic acid 9 mol.%
  • Al compound (I) aromatic carboxylic acid aluminum compound (hereinafter simply called Al compound (I)).
  • Al compound (II) An aromatic carboxylic acid aluminum compound (called Al compound (II)) was prepared in the same manner as in Synthesis Example 1 except for using 75.0 g (ca. 0.3 mol) of 2-amino-3-tert-butyl-5-n-butylbenzoic acid instead of the 3,5-di-tert-butylsalicylic acid.
  • Al compound (III) An aromatic carboxylic acid aluminum compound (called Al compound (III)) was prepared in the same manner as in Synthesis Example 1 except for using 75.0 g (ca. 0.3 mol) of 3-tert-butyl-4-ethoxysalicylic acid instead of the 3,5-di-tert-butylsalicylic acid.
  • Al compound (IV) An aromatic carboxylic acid aluminum compound (called Al compound (IV)) was prepared in the same manner as in Synthesis Example 1 except for using 76.8 g (ca. 0.3 mol) of 3-hydroxy-7-tert-butylnaphthoic acid instead of the 3,5-di-tert-butylsalicylic acid.
  • Zn compound (I) An aromatic carboxylic acid zinc compound (called Zn compound (I)) was prepared in the same manner as in Synthesis Example 1 except for replacing the aluminum sulfate aqueous solution with a zinc sulfate aqueous solution.
  • Ca compound (I) An aromatic carboxylic acid calcium compound (called Ca compound (I)) was prepared in the same manner as in Synthesis Example 1 except for replacing the aluminum sulfate aqueous solution with a calcium chloride aqueous solution.
  • Cr compound (I) An aromatic carboxylic acid aluminum compound (called Cr compound (I)) was prepared in the same manner as in Synthesis Example 1 except for using 80 g (ca. 0.3 mol) of 2-methoxy-3,5-di-tert-butylbenzoic acid instead of the 3,5-di-tert-butylsalicylic acid and using a chromium sulfate aqueous solution instead of the aluminum sulfate aqueous solution.
  • Polyester Resin (1) 100 wt.parts Al compound (I) 5 " Copper phthalocyanine pigment 3 "
  • the above materials were sufficiently preliminarily blended by a Henschel mixer and melt-kneaded through a twin-screw extruder set at 100 °C, followed by cooling, coarse pulverization by a hammer mill, fine pulverization by a fine pulverizer according to the air jet-scheme and classification by a multi-division classifier utilizing the Coanda effect, to obtain cyan-colored toner particles having a weight-average particle size of 5.9 ⁇ m.
  • Cyan Toner (1) To the toner particles, 1.5 wt. % of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane and having a primary particle size of 50 nm were externally added and blended to prepare Cyan Toner (1).
  • the properties of Cyan Toner 1 are summarized in Table 2 appearing hereinafter together with Toners obtained in other Examples described hereinafter.
  • CLC 700 normal temperature/normal humidity
  • LT/LH 10 °C/10 %RH
  • the results are inclusively shown in Tables 4 to 6.
  • the toner provided high-quality images showing high resolution, excellent gradation characteristic and high image density in the respective environment. Good images identical to those in the initial stage were provided even after 20000 sheets of the continuous image formation test. No toner attachment or damages on the photosensitive drum was observed.
  • Image densities were measured by using a Macbeth reflective densitometer (available from Macbeth Co.) with respect to images formed at developing contrast potential differences of 350 volts in LT/LH, 30 volts in NT/NH and 250 volts in HT/HH.
  • Fog (%) was evaluated as a difference in whiteness (reflectance) measured by a reflective densitometer ("REFLECTOMETER", available from Tokyo Denshoku K.K.) between a white ground portion in a copy image and a white transfer paper before image formation.
  • REFLECTOMETER available from Tokyo Denshoku K.K.
  • Resolution was evaluated by forming an original image including 12 types of line images each including 5 lines formed at densities of 2.8, 3.2, 3.6, 4.0, 4.5, 5.0, 5.6, 6.3, 7.1, 8.0, 9.0 and 10.0 lines/mm while keeping a line width and a line spacing equal to each other.
  • a copy image of the original was formed under proper copying conditions and observed through a magnifying glass to determine a largest density image (lines/mm) of which the respective lines could be observed clearly separately. A larger number represents a higher resolution.
  • Toner agglomeration was evaluated by eye observation of an agglomeration state of a toner left standing for 2 months in the high temperature/high humidity environment according to the following standard.
  • Cyan Toners (2) - (5) and Developers (2) - (5) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resins (2) - (5), respectively, instead of Polyester Resin (1).
  • Cyan toner (6) and Developer (6) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (6) and Al compound (II) instead of Polyester Resin (1) and Al compound (I), respectively.
  • Cyan toner (7) and Developer (7) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (7) and Al compound (III) instead of Polyester Resin (1) and Al compound (I), respectively.
  • Cyan toner (8) and Developer (8) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (8) and Al compound (IV) instead of Polyester Resin (1) and Al compound (I), respectively.
  • Cyan toner (9) was prepared in the same manner as in Example 1 except for using a starting material composition obtained by adding 50 wt. parts of fine powder fraction recovered from the multidivision classifier to the starting materials of Example 1. From Cyan Toner (9), Developer (9) was prepared otherwise in the same manner as in Example 1. Developer (9) thus prepared was evaluated in the same manner as in Example 1.
  • Cyan Toner (10) and Developer (10) were prepared and evaluated in the same manner as in Example 1 except for using Zn compound (I) instead of Al compound (I).
  • Cyan Toner (11) and Developer (11) were prepared and evaluated in the same manner as in Example 1 except for using Ca compound (I) instead of Al compound (I).
  • Cyan Toner (12) and Developer (12) were prepared and evaluated in the same manner as in Example 1 except for using Cr compound (I) instead of Al compound (I).
  • Comparative Cyan Toner (1) and Comparative Developer (1) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (9) instead of Polyester Resin (1).
  • Comparative Cyan Toner (2) and Comparative Developer (2) were prepared and evaluated in the same manner as in Comparative Example 1 except for using Zn compound (I) instead of Al compound (I).
  • Comparative Developer (2) exhibited inferior results regarding image stability and fog, and particularly inferior transfer rate and agglomeration in the high temperature/high humidity environment.
  • Comparative Cyan Toner (3) and Comparative Developer (3) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (16) instead of Polyester Resin (1).
  • Comparative Cyan Toner (4) and Comparative Developer (4) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (11) instead of Polyester Resin (1).
  • Comparative Cyan Toner (5) and Comparative Developer (5) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (12) instead of Polyester Resin (1).
  • Comparative Cyan Toner (6) and Comparative Developer (6) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (13) instead of Polyester Resin (1).
  • Comparative Cyan Toner (7) and Comparative Developer (7) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (14) instead of Polyester Resin (1).
  • Comparative Cyan Toner (8) was prepared in the same manner as in Comparative Example 5 except for using a starting material composition obtained by adding 50 wt. parts of fine powder fraction recovered from the multi-division classifier to the starting materials of Comparative Example 5. From Comparative Cyan Toner (8), Comparative Developer (8) was prepared otherwise in the same manner as in Comparative Example 5. Comparative Developer (8) thus prepared was evaluated in the same manner as in Example 1.
  • Comparative Developer (8) provide an initial stage image density of 1.25 and fog of 25 % which were clearly inferior than 1.42 and 0.8 %, respectively, of Comparative Example 5.
  • Comparative Cyan Toner (9) and Comparative Developer (9) were prepared and evaluated in the same manner as in Example 1 except for using Polyester Resin (15) instead of Polyester Resin (1).

Claims (32)

  1. Toner zur Entwicklung elektrostatischer Bilder, umfassend: Tonerteilchen, die wenigstens ein Bindeharz, ein Färbemittel und eine organometallische Verbindung enthalten, worin
    das Bindeharz in den Tonerteilchen einen in Tetrahydrofuran unlöslichen (THF-unlöslichen) Anteil von maximal 5,0 Gew.-%, bezogen auf das Bindeharz, aufweist,
    der Toner eine Glasübergangstemperatur von 50°C bis 80°C aufweist,
    der Toner ein Speichermodul bei 80°C (G'80) von 1×103 bis 5×105 Pa (1×104 bis 5×106 dyn/cm2) aufweist,
    der Toner ein Speichermodul bei 130°C (G'130) aufweist, das ein Verhältnis G'80/G'130 von 10 bis 5×103 bereitstellt, und
    der Toner eine Speichermodulkurve bereitstellt, die ein Minimum (G'min) in einem Temperaturbereich von 110°C bis 190°C aufweist.
  2. Toner nach Anspruch 1, worin das Bindeharz ein THF-unlöslichen Anteil von maximal 1,0 Gew.-% aufweist.
  3. Toner nach Anspruch 1, worin das Bindeharz ein THF-unlöslichen Anteil von maximal 1,0 Gew.-% aufweist und der Toner Eigenschaften des Speichermoduls aufweist, die einschließen:
    ein G'130 von 1×10 bis 5×102 Pa (1×102 bis 5×103 dyn/cm2)
    ein G'min von 5 bis 5×102 Pa (5×10 bis 5×103 dyn/cm2)
    ein Speichermodul bei 200°C (G'200) von
       6×102 bis 1×104 Pa (6×103 bis 1×105 dyn/cm2)
    und
    ein Verhältnis G'200/G'min von 5 bis 100.
  4. Toner nach Anspruch 1, worin das Bindeharz eine Carboxylgruppe oder eine Säureanhydridgruppe aufweist.
  5. Toner nach Anspruch 1, worin die organometallische Verbindung eine Metallverbindung einer aromatischen Carbonsäure ist.
  6. Toner nach Anspruch 1, worin das Bindeharz ein Polyesterharz umfasst.
  7. Toner nach Anspruch 3, worin das Bindeharz ein Polyesterharz umfasst.
  8. Toner nach Anspruch 1, worin das Bindeharz ein Polyesterharz umfasst, das ein Molekülskelett aufweist, das durch die folgende Formel (B) dargestellt ist:
    Figure 00870001
    worin x und y unabhängig voneinander eine ganze Zahl von wenigstens 1 bezeichnen, die ein Mittel von x + y im Bereich von 2 bis 4 bereitstellen.
  9. Toner nach Anspruch 8, worin das Polyesterharz ein nichtlineares Polyesterharz darstellt.
  10. Toner nach Anspruch 8, worin das Polyesterharz eines ist, das einen Peakflächenprozentsatz von 10 bis70 Prozent bereitstellt, der durch die folgende Gleichung berechnet wird: Peakflächenprozentsatz = (AC* / TAC) × 100 (%), worin TAC einen integrierten Wert einer Peakfläche in einem Bereich chemischer Verschiebungswerte (δ-Werte) von 160 ppm bis 1800 ppm (im Bezug auf Tetramethylsilan) darstellt, der dem Carboxylkohlenstoff zuzuordnen ist, und AC* einen integrierten Wert der Peakfläche im δ-Wertebereich von 164,4 bis 164,7 ppm darstellt, wie es mit 13C-NMR gemessen wird.
  11. Toner nach Anspruch 10, worin das Polyesterharz nichtlinear gemacht worden ist, indem es mit einer Polycarbonsäure oder einem mehrwertigen Alkohol umgesetzt worden ist, die beziehungsweise der drei oder mehr funktionelle Gruppen aufweist.
  12. Toner nach Anspruch 1, worin die organometallische Verbindung eine aromatische Carbonsäureverbindung darstellt, die aus einer aromatischen Carbonsäure und einem Metallatom mit einer Valenz von wenigstens 2 gebildet wird.
  13. Toner nach Anspruch 12, worin die organometallische Verbindung eine aromatische Carboxylverbindung darstellt, die aus einer aromatischen Carbonsäure und einem Aluminiumatom gebildet wird.
  14. Toner nach Anspruch 13, worin die aromatische Carbonsäure eine Dialkylsalicylsäure darstellt.
  15. Toner nach Anspruch 14, worin die aromatische Carbonsäure Di-t-butylsalicylsäure darstellt.
  16. Toner nach Anspruch 1, worin die Tonerteilchen 0,1 bis 10 Gewichtsteile der organometallische Verbindung auf 100 Gewichtsteile Bindeharz enthalten.
  17. Toner nach Anspruch 1, worin die Tonerteilchen 0,5 bis 9,5 Gewichtsteile der organometallische Verbindung auf 100 Gewichtsteile Bindeharz enthalten.
  18. Toner nach Anspruch 1, worin das Polyesterharz ein Molekülskelett aufweist, das durch die Formel -C-D-C-D dargestellt ist, worin C
    Figure 00890001
    darstellt (worin x und y ganze Zahlen von wenigstens 1 darstellen) und D
    Figure 00890002
    darstellt, und worin das Polyesterharz nichtlinear gemacht worden ist durch Umsetzen mit einer Polycarbonsäure,, die wenigstens 3 funktionelle Gruppen aufweist.
  19. Toner nach Anspruch 18, worin das Polyesterharz einen Säurewert von 1 bis 30 mgKOH/g aufweist.
  20. Toner nach Anspruch 18, worin das Polyesterharz einen Säurewert von 3 bis 25 mgKOH/g aufweist.
  21. Toner nach Anspruch 1, worin der Toner eine gewichtsmittlere Teilchengröße von 2,5 bis 10,0 um aufweist.
  22. Toner nach Anspruch 1, worin der Toner eine gewichtsmittlere Teilchengröße von 2,5 bis 6,0 um aufweist.
  23. Toner nach Anspruch 1, worin der Toner eine volumenmittlere Teilchengröße von 2,5 bis 6,0 µm aufweist.
  24. Toner nach Anspruch 1, worin der Toner ein Glasübergangstemperatur von 51°C bis 75°C aufweist.
  25. Toner nach Anspruch 1, worin das Bindeharz einen THF-löslichen Anteil enthält, der eine Molekulargewichtsverteilung ergibt, die auf Gelpermeationschromatografie beruht und ein zahlenmittleres Molekulargewicht (Mn) von 1000 bis 9000 und ein Molekulargewicht des Hauptpeaks (Mp) von 5000 bis 12000 bereitstellt.
  26. Toner nach Anspruch 1, worin der THF-lösliche Anteil des Bindeharzes ein nichtlineares Polyesterharz umfasst und eine Molekulargewichtsverteilung ergibt, die ein Verhältnis vom gewichtsmittleren Molekulargewicht (Mw) zum zahlenmittleren Molekulargewicht (Mn) von maximal 5,0 aufweist.
  27. Toner nach Anspruch 1, worin das Bindeharz ein nichtlineares Polyesterharz umfasst, das hergestellt wird, indem ein Bisphenolderivat, das durch die folgende Formel (E) dargestellt ist
    Figure 00900001
    worin x und y ganze Zahlen von wenigstens 1 sind, die ein Mittel x + y im Bereich von 2 bis 4 bereitstellen, mit Fumarsäure in einer Polykondensation umgesetzt wird, um ein Prepolymer zu bilden, und das Prepolymer der Polykondensation mit einem Diol, einer Dicarbonsäure und einer Polycarbonsäure oder einem mehrwertigen Alkohol, die jeweils 3 oder mehr funktionelle Gruppen aufweisen, unterworfen wird.
  28. Toner nach Anspruch 1, worin die Tonerteilchen hergestellt worden sind, indem:
    eine Mischung schmelzgeknetet wird, die wenigstens ein Bindeharz mit einem THF-unlöslichen Anteil von maximal 1,0 Gew.-%, ein Färbemittel und eine organometallische Verbindung aufweist, und
    das sich ergebende, schmelzgeknetete Produkt abgekühlt und dann pulverisiert wird,
    worin das Bindeharz ein nichtlineares Polyesterharz umfasst, das hergestellt wird, indem ein Bisphenolderivat, das durch die folgende Formel (E) dargestellt ist
    Figure 00910001
    worin x und y ganze Zahlen von wenigstens 1 sind, die ein Mittel x + y im Bereich von 2 bis 4 bereitstellen, mit Fumarsäure in einer Polykondensation umgesetzt wird, um ein Prepolymer zu bilden, und das Prepolymer der Polykondensation mit einem Diol, einer Dicarbonsäure und einer Polycarbonsäure oder einem mehrwertigen Alkohol, die jeweils 3 oder mehr funktionelle Gruppen aufweisen, unterworfen wird.
  29. Toner nach Anspruch 28, worin die Tonerteilchen als eine Bindeharzkomponente eine nichtlineares Polyesterharzkomponente enthalten, die durch Quervernetzen des nichtlinearen Polyesterharzes mit einem Metallion erhalten wurde.
  30. Fixierverfahren, umfassend das Fixieren eines Tonerbildes, das auf einem blattförmigen Material getragen wird, auf das blattförmige Material unter Anwendung von Hitze und Druck, wobei das Tonerbild aus einem Toner geformt wird, der Tonerteilchen umfasst, die wenigstens ein Bindeharz, ein Färbemittel und eine organometallische Verbindung enthalten, worin
    das Bindeharz in den Tonerteilchen einen in Tetrahydrofuran unlöslichen (THF-unlöslichen) Anteil von maximal 5,0 Gew.-%, bezogen auf das Bindeharz, aufweist,
    der Toner eine Glasübergangstemperatur von 50°C bis 80°C aufweist,
    der Toner ein Speichermodul bei 80°C (G'80) von 1×103 bis 5×105 Pa (1×104 bis 5×106 dyn/cm2) aufweist,
    der Toner ein Speichermodul bei 130°C (G'130) aufweist, das ein Verhältnis G'80/G'130 von 10 bis 5×103 bereitstellt, und
    der Toner eine Speichermodulkurve bereitstellt, die ein Minimum (G'min) in einem Temperaturbereich von 110°C bis 190°C aufweist.
  31. Fixierverfahren nach Anspruch 30, worin das Tonerbild auf das blattförmige Material fixiert wird, indem eine Heizeinrichtung mit einer Temperatur von 150 ± 30°C auf das blattförmige Material, welches das Tonerbild trägt, gepresst wird.
  32. Fixierverfahren nach Anspruch 30, worin das Tonerbild aus einem Toner nach einem der Ansprüche 2 bis 29 geformt ist.
EP97105412A 1996-04-02 1997-04-01 Toner zur Entwicklung elektrostatischer Bilder und Fixierverfahren Expired - Lifetime EP0800117B1 (de)

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Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3196754B2 (ja) * 1999-02-17 2001-08-06 富士ゼロックス株式会社 静電荷像現像用トナー及びその製造方法、静電荷像現像剤並びに画像形成方法
JP3067761B1 (ja) * 1999-03-04 2000-07-24 富士ゼロックス株式会社 静電荷像現像用トナ―及びその製造方法、静電荷像現像用現像剤並びに画像形成方法
US6326114B1 (en) * 1999-04-14 2001-12-04 Canon Kabushiki Kaisha Toner, and process for producing a toner
EP1059568B1 (de) 1999-06-07 2007-02-14 Canon Kabushiki Kaisha Toner und Bildaufzeichungsverfahren
US6586147B2 (en) 2000-07-10 2003-07-01 Canon Kabushiki Kaisha Toner and full-color image forming method
TWI227384B (en) * 2000-10-12 2005-02-01 Mitsui Chemicals Inc A toner binder for electrophotography and toner for electrophotography
KR100420831B1 (ko) * 2001-07-13 2004-03-02 에스케이케미칼주식회사 폴리에스테르 수지 및 이를 포함하는 토너
US6808852B2 (en) * 2001-09-06 2004-10-26 Canon Kabushiki Kaisha Toner and heat-fixing method
US6929894B2 (en) * 2002-07-10 2005-08-16 Canon Kabushiki Kaisha Toner and fixing method
JP2004264331A (ja) * 2003-01-24 2004-09-24 Sharp Corp マスターバッチ及びそれを用いたトナー
US7396628B2 (en) * 2005-03-15 2008-07-08 Fuji Xerox Co., Ltd. Toner for electrostatic charge image developing, developer for electrostatic charge image developing, and image forming apparatus
JP4914349B2 (ja) * 2005-10-26 2012-04-11 キヤノン株式会社 トナー
US8084178B2 (en) * 2006-01-06 2011-12-27 Canon Kabushiki Kaisha Non-magnetic toner
JP2008101100A (ja) * 2006-10-19 2008-05-01 Fuji Xerox Co Ltd ポリエステル樹脂及びその製造方法、静電荷像現像用トナー、現像装置、カートリッジ、画像形成装置、並びにマイクロリアクタ装置
JP2009098630A (ja) * 2007-09-29 2009-05-07 Konica Minolta Business Technologies Inc 電子写真用トナー、該電子写真用トナーの製造方法、該電子写真用トナーを用いた電子写真用現像剤及び画像形成方法
KR101238365B1 (ko) * 2008-02-21 2013-02-28 삼성전자주식회사 전자사진용 토너
KR101532608B1 (ko) * 2008-12-17 2015-06-30 삼성전자주식회사 정전하 현상용 토너 및 그의 제조방법
CN101876794A (zh) * 2009-04-30 2010-11-03 珠海思美亚碳粉有限公司 显影剂
US9046800B2 (en) 2011-05-12 2015-06-02 Canon Kabushiki Kaisha Magnetic carrier
CN104380207B (zh) 2012-06-22 2019-01-01 佳能株式会社 调色剂
US9116448B2 (en) 2012-06-22 2015-08-25 Canon Kabushiki Kaisha Toner
CN104030918B (zh) * 2014-06-20 2016-04-06 天津市合成材料工业研究所有限公司 金属络合-（3,5-二叔丁基水杨酸）的制备方法
JP6418992B2 (ja) 2015-03-13 2018-11-07 キヤノン株式会社 磁性キャリアおよびその製造方法
JP6700909B2 (ja) 2015-03-31 2020-05-27 キヤノン株式会社 磁性キャリア
JP6584225B2 (ja) 2015-08-25 2019-10-02 キヤノン株式会社 磁性キャリア、二成分系現像剤、補給用現像剤、及び画像形成方法
JP6403816B2 (ja) 2016-02-08 2018-10-10 キヤノン株式会社 磁性キャリア、二成分系現像剤、補給用現像剤、及び画像形成方法
JP6079921B1 (ja) * 2016-03-17 2017-02-15 コニカミノルタ株式会社 トナー
US10289016B2 (en) * 2016-12-21 2019-05-14 Canon Kabushiki Kaisha Toner
US10409188B2 (en) 2017-02-10 2019-09-10 Canon Kabushiki Kaisha Magnetic carrier, two-component developer, replenishing developer, and image forming method
US10451985B2 (en) 2017-02-28 2019-10-22 Canon Kabushiki Kaisha Toner
JP6938345B2 (ja) 2017-11-17 2021-09-22 キヤノン株式会社 トナー
JP7293009B2 (ja) 2018-08-08 2023-06-19 キヤノン株式会社 磁性キャリア、二成分系現像剤、補給用現像剤、及び画像形成方法
JP7293010B2 (ja) 2018-08-08 2023-06-19 キヤノン株式会社 磁性キャリア、二成分系現像剤、補給用現像剤、及び画像形成方法
JP7171314B2 (ja) 2018-08-28 2022-11-15 キヤノン株式会社 トナー
JP7130518B2 (ja) 2018-09-28 2022-09-05 キヤノン株式会社 磁性キャリア、二成分系現像剤、補給用現像剤、及び画像形成方法
JP7210222B2 (ja) * 2018-10-19 2023-01-23 キヤノン株式会社 トナー
US11249410B2 (en) 2018-12-12 2022-02-15 Canon Kabushiki Kaisha Toner

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2297691A (en) * 1939-04-04 1942-10-06 Chester F Carlson Electrophotography
CA1054421A (en) * 1973-07-18 1979-05-15 Thomas A. Jadwin Electrographic developing composition and process
JPS556895B2 (de) * 1974-04-10 1980-02-20
US4162428A (en) * 1978-06-29 1979-07-24 Westinghouse Electric Corp. Variable inductance ballast apparatus for HID lamp
FR2465985A1 (fr) * 1979-09-25 1981-03-27 Ceraver Structure alveolaire monolithique a grande surface de contact
JPS5698202A (en) * 1980-01-07 1981-08-07 Mitsubishi Rayon Co Ltd Resin for toner of electronic photography
JPS5911902B2 (ja) * 1980-08-15 1984-03-19 コニカ株式会社 静電荷像現像用トナ−
JPS61213858A (ja) * 1985-03-20 1986-09-22 Canon Inc 静電荷像現像用トナ−
JPS6430061A (en) * 1987-07-27 1989-01-31 Hitachi Ltd Automatic loader for optical disk
JP2649695B2 (ja) * 1988-05-23 1997-09-03 コニカ株式会社 静電像現像剤
JPH01302267A (ja) * 1988-05-30 1989-12-06 Konica Corp 静電像現像剤
JPH0396964A (ja) * 1989-09-11 1991-04-22 Konica Corp 画像形成方法
CA2029468C (en) * 1989-11-09 1997-01-28 Tsutomu Kukimoto Toner, image forming apparatus, apparatus unit and facsimile apparatus
JP2932195B2 (ja) * 1989-12-29 1999-08-09 キヤノン株式会社 電子写真用トナー
JPH0424648A (ja) * 1990-05-18 1992-01-28 Fuji Xerox Co Ltd 磁性トナー
US5330871A (en) * 1990-11-29 1994-07-19 Canon Kabushiki Kaisha Toner for developing electrostatic image
JP2747126B2 (ja) * 1991-05-31 1998-05-06 三田工業株式会社 電子写真用トナー
JP3119752B2 (ja) * 1992-12-09 2000-12-25 コニカ株式会社 カラートナー
CA2139186C (en) * 1993-12-29 1997-12-02 Takaaki Kohtaki Toner for developing electrostatic image

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KR970071155A (ko) 1997-11-07
CN1106591C (zh) 2003-04-23
US5851714A (en) 1998-12-22
KR100228054B1 (ko) 1999-11-01
HK1002875A1 (en) 1998-09-25
CN1171567A (zh) 1998-01-28
DE69702798D1 (de) 2000-09-21

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